Perfluoralkyl anion/perfluoroalkyl cation ion pair complexes

ABSTRACT

The instant invention relates to the use of ion-pair complexes derived from anionic perfluoroalkyl sulfonates, carboxylates, phosphates and phosphonates and cationic perfluoroalkyl surfactants. Such complexes are capable of reducing the surface tension of aqueous solutions dramatically even at extremely low concentrations, and are useful as wetting, spreading and leveling agents and are especially preferred as components in so-called aqueous film forming foam compositions for fighting polar and non-polar solvent and fuel fires.

BACKGROUND OF THE INVENTION

It is well known that conventional hydrocarbon surfactants can lower thesurface tension of aqueous solutions to as low as 23 dynes/cm, whilefluorinated surfactants can attain surface tensions in the 15 to 20dynes/cm range. While fluorinated surfactants have proven to be muchmore efficient as surface tension depressants than hydrocarbonsurfactants, their use has has been severely limited because of theirhigh cost. The problem of attaining lowest possible surface tension withthe smallest possible amount of highly priced fluorinated surfactants orsurfactant/synergist systems has been the subject of many patents andpublications. It is an object of the present invention to provide novelperfluoralkyl or R_(f) R_(f) ion pair complexes which are capable ofreducing the surface tension of aqueous systems to levels which arebelow the surface tensions achieved with equal amounts of the individualanionic and cationic perfluoroalkyl surfactants from which the novelR_(f) R_(f) ion-pair complexes are derived.

Four general classes of surfactants are commonly represented as usefulsurface tension depressants, namely cationic, anionic, amphoteric andnonionic surfactants. In many applications, combinations of hydrocarbonsurfactants are used in order to achieve certain results. It isgenerally known that nonionic and amphoteric surfactants can be used incombination with each other as well as in combination with either anioicsurfactants or cationic surfactants. Such surfactant mixtures are saidto be compatible. It is also generally known that anionic and cationicsurfactants should not be used in combination with each other, becausethey are incompatible. The reason combinations of anionic and cationicare called incompatible is that they react with each other and formpoorly soluble hydrocarbon-hydrocarbon complexes plus salts, asdescribed in Kirk-Othmer, Encyclopedia of Chemical Technology, 19, 555,2nd Ed., (1966) and Milton J. Rosen, Surfactants and InterfacialPhenomena, J. Wiley, 24.

These hydrocarbon cation/hydrocarbon anion complexes are simply referredto as R_(h) R_(h) complexes and have been described by Hummel aselectroneutral substances. See Hummel, D., Identification and Analysisof Surface-Active Agents, Interscience, New York 1962 (p. 23). It hasbeen reported that certain mixtures of hydrocarbon type anionic andcationic surfactants in some cases can exhibit low surface tensions.Corkill, see J. M. Corkill et al., Proc. Roy. Soc. (London) Series A273(1963), was the first to show that mixtures of sodium decyl sulfate anddecyltrimethylammonium bromide or the ion-pair hydrocarbon saltdecyltrimethylammonium decyl sulfate give virtually identical surfacetension-concentration curves and surface tension values as low as 22dynes/cm.

Mannheimer (U.S. Pat. No. 3,661,945) showed that select structural typesof anionics and cationics could give useful reaction products.

L. G. Anello and R. F. Sweeney (U.S. Pat. No. 3,839,343) has reportedthe preparation of a symmetrical polyfluoroisoalkoxyalkyl quaternaryammonium sulfates--[(CF₃)₂ CFO(CF₂)_(s) (CH₂)_(t) NR_(x) ].sup.⊕ O.sup.⊖SO₂ O(CH₂)_(t) (CF₂)_(s) OCF(CF₃)₂.

It has now been surprisingly found that R_(f) R_(f) ion-pair complexesmade by reacting equimolar amounts of specific classes of anionic andcationic R_(f) -surfactants are extremely useful and efficient surfacetension depressants even though such R_(f) R_(f) complexes have beenfound to be very much less soluble than the anionic and cationicsurfactants from which they were derived, and are in most casespractically insoluble in water (solubility of less than 0.001% byweight).

Most importantly, it was found that stable dispersions of thewaterinsoluble R_(f) R_(f) ion-pair complexes can be made and, quitesignificantly, it was found that such R_(f) R_(f) ion-pair complexdispersions provide considerably lower surface tension properties inwater at extremely low concentrations than did equal amounts of eitherthe anionic or cationic fluorochemical surfactants from which the R_(f)R_(f) ion-pair complex was derived.

Furthermore, it was found that the novel R_(f) R_(f) ion-pair complexesare most useful as additives to so-called AFFF agents or aqueous filmforming foams. These so-called AFFF agents act in two ways:

(a) As aqueous foams they are used as primary fire extinguishing agents,and

(b) As vapor sealants they prevent the reignition of fuels and solvents.It is this second property which makes AFFF agents far superior to otherknown fire fighting agents for fighting fuel and solvent fires. Thisvapor sealing action of an AFFF agent is achieved by the spreading ofthe aqueous AFFF agent solution over the fuel surface.

The criterion necessary to attain spontaneous spreading of twoimmiscible phases has been taught by Harkins et al., J. Am. Chem. 44,2665 (1922). The measure of the tendency for spontaneous spreading isdefined by the spreading coefficient (SC) as follows:

    SC=δa-δb-δi

where

SC=spreading coefficient

δa=surface tension of the lower liquid phase

δb=surface tension of the upper aqueous phase

δi=interfacial tension between the aqueous upper phase and lower liquidphase

If the SC is positive, the solution should spread and film formationshould occur. The greater the SC, the greater the spreading tendency.This requires the lowest possible aqueous surface tension and lowestinterfacial tension.

Based on the Harkins equation it is obvious that the most efficientsurface tension depressants and interfacial tension depressants willyield aqueous film forming foams with the highest spreading coefficient.

Aqueous solutions with very low surface tensions used for theextinguishment of hydrocarbon fuel fires were first disclosed by N. O.Brace in U.S. Pat. No. 3,047,619 and 3,091,614. Brace utilized sprays ofaqueous solutions containing R_(f) surfactants of thebeta-hydroperfluoroalkyl type. Similarly, Tuve, et al., disclosed theuse of aqueous solutions containing R_(f) -surfactants derived fromperfluorinated acids of the R_(f) COOH and R_(f) SO₃ H type as firefighting foams in U.S. Pat. No. 3,258,423.

While R_(f) -surfactants reduce the surface tension of aqueous solutionsto as low as 15 dynes/cm, they generally do not reduce interfacialtension properties to the same degree as many hydrocarbon surfactants.

Aqueous solutions containing R_(f) -surfactants and hydrocarbonsurfactants having very low surface tensions as well as low interfacialtension properties, and therefore a positive spreading coefficient whenmeasured against hydrocarbon solvents, were prepared by Klevens andRaison, J. Chim. Phys., 51, p. 1-8 (1959). The 3M Company, amanufacturer of R_(f) -surfactants, recommended in their technicalbulletins (3M Brand Fluorochemical Surfactants, June 15, 1963, pp. 1-45)the combination of R_(f) -surfactants and hydrocarbon surfactants toachieve low surface tension and low interfacial tension in aqueoussolutions and therefore a positive spreading coefficient.

Solutions of fluorochemical surfactants and hydrocarbon surfactants wereused the first time by Ratzer as fire fighting foams and disclosed atthe "Fourth Quinquennial Symposium on Fire Fighting Foam", Aug.11/12/13, 1964 at Campobello, and published in the minutes of the abovesymposium, and in "Foam" October 1964, No. 24 (a publication of theMearl Corporation, Ossining, N.Y.). Drs. Shinoda and Fujihira reportedthe use of mixtures of fluorochemical and hydrocarbon surfactants in thecontext of various commercial applications including fire extinguishingagents at a Meeting on the Research on Oil sponsored by the Japan OilChemists' Society and the Chemical Society of Japan Chemistry on Nov.2-3, 1966 at Nagoya, Japan. Fire fighting agents based on aqueoussolutions containing fluorochemical surfactants and hydrocarbonsurfactants, as disclosed the first time by Ratzer are today commonlyknown as AFFF agent or Aqueous Film Forming Foams. Many U.S. Pat. Nos.disclosing AFFF agent compositions based on fluorochemical surfactantsand hydrocarbon surfactants have since issued, such as 3,047,619;3,257,407; 3,258,423; 3,562,156; 3,621,059; 3,655,555; 3,661,776;3,677,347; 3,759,981; 3,772,195; 3,798,265; 3,828,085; 3,839,425;3,849,315; 3,941,705; 3,952,075; 3,957,657; 3,957,658; 3,963,776;4,038,195; 4,042,522; 4,049,556; 4,060,132; 4,060,489; 4,069,158;4,090,967; 4,099,574; 4,149,599; 4,203,850; 4,209,407.

In U.S. Pat. No. 4,089,804, R. A. Falk discloses a method to improveR_(f) -surfactants by employing water-insoluble R_(f) -synergists, andin U.S. Pat. No. 4,090,967, AFFF agents are disclosed by Falk whichcontain R_(f) -surfactants, R_(f) -synergists and hydrocarbonsurfactants among other ingredients. With the help of water insolubleR_(f) -synergists it has now become not only possible to reduce thecontent of the costly R_(f) -surfactants in an AFFF agent by up to 50%(and still meet U.S. military specifications for AFFF agents), but italso became possible to improve and utilize certain R_(f) -surfactantsin AFFF agent compositions which in the absence of the novelwater-insoluble R_(f) -synergists would not provide aqueous solutionswith positive spreading coefficients.

However, a deficiency in prior-art AFFF agents continues to be (a) theamount of high priced fluorochemical required to achieve the properperformance, which limits the use of AFFF agents and (b) the inherentfish toxicity due to the high surfactant content in AFFF agents.

Since the AFFF agents ultimately enter the aquatic ecosystem, it hasbeen customary to choose at least one or two aquatic species to assesspotential aquatic toxicity and extrapolate generally two other species.The U.S. Navy screens AFFF agents toxicity on the Mummichog (fundulusheteroclitus) in artificial sea water. Agents are compared by 96 houractive exposure tests to determine the concentration lethal to 50% ofthe organisms; this is the 96 hour median lethal concentration or LC₅₀.

It has now been found that the novel R_(f) R_(f) ion-pair complexes arepartial or complete substitutes for the fluorochemical surfactants usedin prior-art AFFF agents which will (a) reduce cost due to the use ofsmaller amounts of the more efficient ion-pair complexes, (b) willincrease the efficiency of the AFFF agents and (c) reduce the fishtoxicity significantly.

DETAILED DISCLOSURE

The instant invention relates to hydrolytically stable R_(f) R_(f)ion-pair complexes having the formula:

    R.sub.f --A--Q.sup.⊖.N.sup.⊕ (R.sub.1)(R.sub.2)(R.sub.3)--A'--R.sub.f '

wherein

R_(f) and R'_(f) independently represent straight or branched chainperfluoroalkyl of 4 to 18 carbons;

A and A' independently represent a divalent covalent linking group ofunrestricted structure, but is typically a straight or branchedsubstituted or unsubstituted aliphatic chain of 1 to 18 atoms and mayinclude either, sulfide, sulfone, sulfoxide, trivalent nitrogen atomsbonded only to carbon atoms, carbonyl, sulfonamido, carbonamido, arylenegroups and the like, with the proviso that A may be a direct bond, butA' must contain at least 1 carbon atom;

Q represents carboxylate, sulfonate, phosphate and phosphonate.

R₁, R₂ and R₃ are independently hydrogen, phenyl, or alkyl of 1 to 8carbon atoms which are unsubstituted or substituted by halo, hydroxy oraryl, --CHR₄ CH₂ O)_(y) R₅ where y is 1 to 20, R₄ is hydrogen or alkylof 1 to 4 carbon atoms, R₅ is hydrogen or methyl, or

R₁ and R₂ taken together with the nitrogen to which they are attachedrepresent piperidino, morpholino, or piperazino; or

wherein R₁, R₂ and R₃ taken together with the nitrogen to which they areattached represent pyridinium, or substituted pyridinium ##STR1## Apreferred class of complexes are those of the above formula whereinR_(f) is perfluoroalkyl of 4 to 12 carbon atoms;

A and A' independently represent a divalent covalent linking group ofthe formula

    --(G).sub.n.sbsb.1 --alkylene--(G'--alkylene).sub.n.sbsb.2 (G"--alkylene).sub.n.sbsb.3

wherein

G, G' and G" independently represent --O--, --S--, --SO₂ --, --SO₂ NH--,##STR2## n₁ is 0 or 1; n₂ and n₃ are independently 0, 1 or 2;

alkylene is straight or branched chain alkylene of 1 to 8 carbon atoms,with the proviso that each aliphatic chain A and A' contains no morethan 18 carbon atoms and the R_(f) and R_(f) ' group, respectively, isbonded to the left hand side of said covalent linking group,

and A additionally represents a direct bond;

R₁, R₂ and R₃ are lower alkyl; and

Q is carboxylate, sulfonate, phosphate or phosphonate.

Highly preferred are those within said preferred class wherein R_(f) isperfluoralkyl of 4 to 12 carbon atoms;

A and A' independently represent

--CH₂ CH₂ --S--alkylene--G'--alkylene-- wherein G' is --SO₂ NH-- or##STR3## and each alkylene is straight or branched chain of from 1 to 6carbon atoms;

R₁, R₂ and R₃ are methyl; and

Q is carboxylate, sulfonate, phosphate or phosphonate.

Most highly preferred are those complexes wherein

Q is sulfonate, carboxylate or phosphate.

The instant R_(f) R_(f) ion-pair complexes are derived from anionic andcationic fluorochemical surfactants according to the following equation:

    R.sub.f --A--Q.sup.⊖ ·M.sup.⊕ +R.sub.f '--A--N.sup.⊕ (R.sub.1)(R.sub.2)(R.sub.3)·X.sup.⊖ →R.sub.f --A--Q.sup.⊖ ·N.sup.⊕ (R.sub.1)(R.sub.2)(R.sub.3)--A'--R.sub.f '+M.sup.⊕ X.sup.⊖

wherein R_(f), R_(f) ', A, A', Q, R₁, R₂ and R₃ are previously describedand M is an aqueous solvatable cation such as hydrogen, alkali oralkaline earth metal cation, tetramethyl ammonium or other simplequaternary ammonium cation and X is an aqueous solvatable anion such aschloride, bromide, iodide, methyl sulfate and the like.

The synthesis of the R_(f) R_(f) ion-pair complexes can be carried outin several ways.

One method consists of reacting equimolar amounts of concentratedaqueous solutions of the respective anionic and cationic R_(f)surfactants. These complexes will precipitate from the concentratedsolutions and can be filtered, washed and dried. This method yields thecomplexes in solid form, substantially free from (a) trace amounts ofunreacted surfactants, surfactant precursors and (b) free from saltsformed during the reaction.

A second method consists of reacting equimolar amounts of the respectivesurfactants in a solvent-water mixture. It was found that in a preferredsolvent-water mixture high solid content dispersions of the novelcomplexes can be obtained which have shown to possess good stability.This method of synthesis is a preferred method if removal of (a) traceamounts of unreacted surfactants and surfactant precursors and (b)removal of the salt formed during the reaction is not necessary. It wasfound that such high solid content dispersions will precipitate ifdiluted with water. However, it was also found that blending such highsolid content complex dispersions with micelle forming surfactants priorto dilution with water can prevent such precipitation. Similarly,dilution of high solid content dispersions with selected solvents orsolvent-water mixtures can prevent precipitation of the water-insolublecomplexes.

A third synthesis involves the reaction of anionic and cationicsurfactant solutions in which either the anionic or the cationicsurfactant is present in a higher than equimolar amount. As a result amixture of a R_(f) R_(f) ion-pair complex and an anionic or cationicsurfactant will be formed, which will have increased stability even ifdiluted to lower concentrations with water. Instead of carrying out theabove described reaction with an excess amount of either the anionic orcationic surfactant, it is also possible to carry out the reaction withequimolar amounts of anionic and cationic surfactant in the presence ofsufficient amounts of a micelle forming nonionic or amphotericsurfactant in order to prevent precipitation of high solid contentdispersions upon dilution with water.

A fourth method, ideal for laboratory purposes, yielding very purecomplexes is based on the reaction of anionic and cationic surfactantsin a dialysis cell. By selecting the proper dialysis membranes,unreacted surfactant, precursors and salts formed during the complexformation as well as solvents will diffuse through the membrane, leavinganalytically pure complexes as precipitates or solutions in the dialysiscell.

The individual anionic and cationic fluorochemical surfactants which areused to make the R_(f) R_(f) ion-pair complexes are known compounds, perse, and a number of useful anionic and cationic fluorochemicalsurfactants are sold commercially by the following companies under thefollowing trade names:

Asahi glass (Surflon S-); Bayer (FT-Typen); CIBA-GEIGY (LODYNE);Dainippon Inc. (Magafac); DuPont (Zonyl); Hoechst (Licowet, Fluorwet);I.C.I. (Monflor); Neos (Ftergent); Tohaku Hiryo (F-Top); Ugine-Kuhlman(Forofac); 3M (Fluorad).

Illustrative examples of anionic and cationic fluorochemical surfactantsused for the synthesis of the instant R_(f) R_(f) ion-pair complexes aredisclosed in the following patents and are herein incorporated byreference in toto:

U.S. Pat. Nos. 2,727,923; 2,759,019; 2,764,602; 2,764,603; 3,147,065;3,147,066; 3,207,730; 3,257,407; 3,350,218; 3,510,494; 3,681,441;3,759,981; 3,836,552; 3,933,819; 4,014,926; 4,062,849 and 4,098,811;

German Offen. Nos. 2,013,104; 2,224,653; 2,357,916; 2,732,555;1,925,555; 2,127,232; 2,230,366; 2,236,729; 2,337,638 and 2,523,402;

French Pat. Nos. 2,035,589; 2,241,542 and 2,333,564;

Belgium Pat. Nos. 788,335 and 801,585;

British Pat. Nos. 1,270,622; 1,288,678 and 1,435,200.

Other illustrative examples of R_(f) -surfactants which can be used forthe synthesis of the R_(f) R_(f) ion-pair complexes are the below shownacids and their alkali metal salts. Preferred anionic groups arecarboxylate, phosphate and sulfonate. The anionic surfactant may be usedas free acid, an alkali metal salt thereof, ammonium or substitutedammonium. The patent numbers appearing in parenthesis are patents whichmore fully disclose the represented clss of compounds. The disclosuresof these patents are incorporated herein by reference.

    ______________________________________                                        Carboxylic Acids and Salts Thereof                                            R.sub.f COOH        (Scholberg el at., J. Phys.                                                   Chem. 57,923-5 (1953)                                     R.sub.f (CH.sub.2).sub.1-20 COOH                                                                  (Ger. 1,916,669)                                          R.sub.f O(CH.sub.2).sub.1-20 COOH                                                                 (U.S. Pat. No. 3,409,647)                                 R.sub.f SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 COOH                                                  (U.S. Pat. No. 3,258,423)                                 (C.sub.2 F.sub.5).sub.2 (CF.sub.3)CCH.sub.2 COOH                                                  (Brit. 1,176,493)                                         C.sub.10 F.sub.19 OC.sub.6 H.sub.4 CON(CH.sub.3)CH.sub.2 COOH                                     (Brit. 1,270,662)                                         R.sub.f (CH.sub.2).sub.1-3 SCH(COOH)CH.sub.2 COOH                                                 (U.S. Pat. No. 3,706,787)                                 R.sub.f (CH.sub.2).sub.1-12 S(CH.sub.2).sub.1-17 COOH                                             (Ger. 2,239,709;                                                              U.S. Pat. No. 3,172,910)                                  Sulfonic Acids and Salts Thereof                                              R.sub.f SO.sub.3 H  (U.S. Pat. No. 3,475,333)                                 R.sub.f C.sub.6 H.sub.4 SO.sub.3 H                                                                (Ger. 2,134,973)                                          R.sub.f (CH.sub.2).sub.1-20 SO.sub.3 H                                                            (Ger. 2,309,365)                                          R.sub.f SO.sub.2 NHCH.sub.2 C.sub.6 H.sub.4 SO.sub.3 H                                            (Ger. 2,315,326)                                          R.sub.f SO.sub.2 N(CH.sub.3)(C.sub.2 H.sub.4 O).sub.1-20 SO.sub.3                                 (S.A. 693,583)                                            R.sub.f CH.sub.2 CH.sub.2 OCH.sub. 2 CH.sub.2 CH.sub.2 SO.sub.3 H                                 (Can. 842,252)                                            R.sub.f OC.sub.6 H.sub.4 SO.sub.3 H                                                               (Ger. 2,230,366)                                          C.sub.12 F.sub.23 OC.sub.6 H.sub.4 SO.sub.3 H                                                     (Ger. 2,240,263)                                          (C.sub.2 F.sub.5).sub.3 CO(CH.sub.2).sub.3 SO.sub.3 H                                             (Brit. 1,153,854)                                         CF.sub.3 (C.sub.2 F.sub.5).sub.2 CO(CH.sub.2).sub.3 SO.sub.3 H                                    (Brit. 1,153,854)                                         (C.sub.2 F.sub.5).sub.2 (CF.sub.3)CCH═C(CF.sub.3)SO.sub.3 H                                   (Brit. 1,206,596)                                         R.sub.f (CH.sub.2).sub.1 or .sub.2 O--(C.sub.2 H.sub.4 O).sub.1-12            --SO.sub.3 H        (Ger. 2,310,426)                                          Phosphonates, Phosphates,                                                     Related Phosphoro Derivatives                                                 R.sub.f PO(OH).sub.2                                                                              (Ger. 2,110,767)                                          R.sub.f SO.sub.2 N(Et)C.sub.2 H.sub.4 OPO(OH).sub.2                                               (Ger. 2,125,836)                                          R.sub.f CH.sub.2 OPO(OH).sub.2                                                                    (Ger. 2,158,661)                                          C.sub.8 F.sub.15 OC.sub.6 H.sub.4 CH.sub.2 PO(OH).sub.2                                           (Ger. 2,215,387)                                          R.sub.f OC.sub.6 H.sub.4 CH.sub.2 PO(OH).sub.2                                                    (Ger. 2,230,366)                                          ______________________________________                                    

The commercially available surfactants used in the following examplesare:

FC-95, which is an alkali metal salt of perfluoroalkylsulfonic acid; CASRegistry No. 2795-39-3; C₈ HF₁₇ O₃ S.K.

FC-128, which is a perfluoroalkanesulfonamido alkylenemonocarboxylicacid salt as disclosed in U.S. Pat. No. 2,809,990; C₁₂ H₈ F₁₇ NO₄ S.K;CAS Registry No. 2991-51-7.

FC-134, which is a cationic quaternary ammonium salt derived from aperfluoroalkanesulfonamidoalkylenedialkylamine as disclosed in U.S. Pat.No. 2,759,019; C₁₄ H₁₆ F₁₇ N₂ O₂ S.I: CAS Registry No. 1652-63-7.

Zonyl FSC, a cationic quaternary ammonium salt derived from linearperfluoroalkyl telomers.

Zonyl FSA and FSP, anionics derived from linear perfluoroalkyl telomers.

Monflor 31 and 32, anionics derived from branched tetrafluoroethyleneoligomers as disclosed in GB Pat. No. 1,148,486.

Monflor 72, a cationic derived from branched tetrafluoroethyleneoligomers as disclosed in DT Pat. No. 2,224,653.

The following Table 1 illustrates how a selected type of an R_(f) R_(f)ion-pair complex differs in its properties from the precursor anionicand cationic fluorochemical surfactants. Besides the differences shownin Table 1 (solubility, melting point, surface tension), R_(f) R_(f)ion-pair complexes also differ in many other properties from theirprecursor surfactants.

                                      TABLE 1                                     __________________________________________________________________________     Physical Properties of R.sub.f R.sub.f Complexes and                         The Surfactants From Which They are Prepared                                                Anionic Cationic                                                Physical Properties                                                                         R.sub.f --Surfactant.sup.1                                                            R.sub.f --Surfactant.sup.2                                                             R.sub.f R.sub.f --Complex.sup.3                __________________________________________________________________________    Melting Point ° C.                                                                   ˜208-211                                                                        Too hygroscopic                                                                        ˜148-155                                                       to determine                                            Solubility in water % by wt.                                                                >1      >1       ≃0.001                           Surface tensions in                                                           Deionized water (dynes/cm                                                     Concentration 0.001% by wt.                                                                 42.0    41.7     26.9                                           0.01% by wt.  24.5    24.4     16.1.sup.4                                     __________________________________________________________________________     .sup.1 R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 CONHC(CH.sub.3).sub.2     CH.sub.2 SO.sub.3.sup.⊖                                               .sup.2 R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2 CH(OH)CH.sub.2 N.sup.⊕         (CH.sub.3).sub.3 Cl.sup.                                                      .sup.3 R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 CONHC(CH.sub.3).sub.2     CH.sub.2 SO.sub.3.sup.⊖ N.sup.⊕ (CH.sub.3).sub.3 CH.sub.2         CH(OH)CH.sub.2 SCH.sub.2 CH.sub.2                                             R.sub.f = C.sub.6 F.sub.13 and C.sub.8 F.sub.17 (1:1 by wt.)                  .sup.4 Aqueous solution with 0.01% by wt. of R.sub.f R.sub.f complex is       supersaturated and will form a precipitate after standing for several         hours                                                                    

Such other properties include foaming (Ross-Miles Test), wetting(Draves-Clarkson Test), CMC (Critical Micelle Concentration), ionizationconstants, etc.

The instant R_(f) R_(f) ion-pair complexes, preferably in the form ofaqueous dispersions, are very efficient surface tension suppressants andare useful in many applications where improved wetting, spreading andleveling is required. Because R_(f) R_(f) ion-pair complexes are neutralspecies, they are compatible with nonionic, amphoteric, anionic andcationic surfactants, be they of the hydrocarbon or fluorocarbon type,as well as fluorochemical synergists as described in U.S. Pat. No.4,089,804. It was also found that the instant R_(f) R_(f) ion paircomplexes do impart oil and water repellency to substrates such astextiles, fibers, nonwovens and paper. However, the preferred utility ofthe novel R_(f) R_(f) ion-pair complexes is in the field of aqueous filmforming foams ro so-called AFFF agents used in fighting polar andnon-polar solvent and fuel fires. As will be shown in the experimentalpart, R_(f) R_(f) ion-pair complexes can be successfully used asadditives to AFFF agent compositions as disclosed in, but not limitedto, U.S. Pat. Nos.: 3,047,619; 3,257,407; 3,258,423; 3,562,156;3,621,059; 3,655,555; 3,661,776; 3,677,347; 3,759,981; 3,772,195;3,798,265; 3,828,085; 3,839,425; 3,849,315; 3,941,705; 3,952,075;3,957,657; 3,957,658; 3,963,776; 4,038,195; 4,042,522; 4,049,556;4,060,132; 4,060,489; 4,069,158; 4,090,967; 4,099,574; 4,149,599;4,203,850; 4,209,407.

As additives to prior-art AFFF agents the novel R_(f) R_(f) ion-paircomplexes will generally increase the spreading coefficient andtherefore fire fighting performance and will reduce, in addition, fishtoxicity of the AFFF agent. Rather than using the R_(f) R_(f) ion-paircomplexes as additional additives to prior art AFFF agent compositionsit is recommended to use the ion-pair complexes as partial or completesubstitutes for the fluorochemical surfactants present in the prior-artAFFF agent. Since it is possible to substitute larger quantities offluorochemical surfactants with smaller quantities of the highlyefficient R_(f) R_(f) ion-pair complexes, it is possible to reduce thecost of the AFFF agent without reducing performance.

Commercial AFFF agents are primarily used today in so-called 6%, 3% and1% proportioning systems. This means that 6, 3 or 1 part of an AFFFagent concentrate are diluted (proportioned) with 94, 97 or 99 parts ofwater (fresh, sea or brackish water) and applied by conventional foammaking equipment. Preferred AFFF agent concentrates based on the novelR_(f) R_(f) ion-pair complexes useful for 6, 3 and 1% proportioningcomprise the following components, numbered D through M:

D. 0.05 to 5% by weight of an R_(f) R_(f) ion-pair complex of the typeR_(f) -A-Q.sup.⊖.N.sup.⊕ (R₁)(R₂)(R₃)-A'-R_(f) ' and

E. 0 to 25% by weight of nonionic, amphoteric, anionic or cationicfluorochemical surfactants

F. 0 to 55 of a fluorochemical synergist

G. 0 to 40% by weight of a hydrocarbon surfactant

H. 0 to 70% by weight of a water miscible solvent;

I. 0 to 5% by weight of an electrolyte;

K. 0 to 10% by weight of a polymeric foam stabilizer;

L. 0 to 10% by weight of a polysaccaride, and

M. Water in the amount to make up the balance of 100%.

A preferred R_(f).R_(f) complex (Compound D) is represented by theformula: ##STR4## where R₆ is hydrogen or lower alkyl; each of R₇, R₉and R₁₀ is individually hydrogen or alkyl group of 1-12 carbons; R₈ ishydrogen, alkyl of 1 to 12 carbons, phenyl, tolyl, and pyridyl; and R₁₁is branched or straight chain alkylene of 1 to 12 carbon atoms,alkylenethioalkylene of 2 to 12 carbon atoms, alkyleneoxyalkylene of 2to 12 carbon atoms or alkyleneiminoalkylene of 2 to 12 carbon atomswhere the nitrogen atom is secondary or tertiary.

Preferred fluorochemical surfactants (Component E) are broadly chosenfrom among anionic, nonionic, amphoteric or cationic R_(f) surfactantsas cited in U.S. Pat. No. 4,090,967, incorporated herein by referenceand in pending application U.S. Ser. No. 129,872 (Mar. 13, 1980).

Preferred are: ##STR5## the foam stabilizing oligomeric surfactants offormula R_(f) -E-S-[M₁ ]_(x) [M₂ ]_(y) H and mixtures thereof which maybe incorporated to improve burnback resistance and resistance to fuelpenetration. These oligomers as well as their preparation are more fullydescribed in assignee's copending application Ser. No. 129,872 filedMar. 13, 1980 by E. Kleiner, T. Cooke and R. Falk, the disclosure ofwhich is incorporated herein.

Preferred is an oligomer wherein R_(f) is a straight chainperfluoroalkyl of 6 to 14 carbon atoms, E is ethylene, --[M₁ ]-- is##EQU1## x is 3 to 50 and y is 0

The structures of the fluorinated synergists (Component F) may be chosenfrom compounds represented by the formula

    R.sub.f --T.sub.m --Z

as described and defined in U.S. Pat. No. 4,090,167 incorporated hereinby reference. Illustrative examples of R_(f) -synergists which can beused in the compositions of this invention also include

R_(f) SO₂ NH₂,

R_(f) SO₂ N(CH₂ CH₂ OH)₂,

R_(f) SO₂ N(C₂ H₅)CH₂ CHOHCH₂ OH,

R_(f) CH₂ CH₂ SCH₂ CH₂ CONH₂,

R_(f) CH₂ OH,

R_(f) CH₂ CHOHCH₂ OH, and

R_(f) CHOHCH₂ OH, where R_(f) is perfluoroalkyl of 4 to 12 carbon atoms.

The hydrocarbon surfactant component G is broadly chosen from ionic,amphoteric and nonionic surfactants as described in U.S. Pat. No.4,090,967.

Suitable hydrocarbon anionic surfactants include C₈ -C₁₄ -alkylcarboxylic acids and salts thereof, C₈ -C₁₄ -alkyl hydrogen sulfates andthe corresponding sulfonic acids and salts thereof. C₈ -C₁₄ -alkylethoxy sulfates and salts thereof, alpha olefin sulfonates of 6 to 14carbon atoms, C₈ -C₁₄ -alkyl amido alkylene sulfonates, and the like.Preferred are carboxylic or sulfonic acids as they are hydrolyticallystable.

Suitable amphoteric hydrocarbon surfactants are those which contain inthe same molecule, amino and carboxy, sulfonic acid, sulfuric ester orthe like. Higher alkyl (C₆ -C₁₄) betaines and sulfobetaines areincluded. Most preferred amphoteric hydrocarbon surfactants are the C₆-C₁₆ -alkyl amino C₂ -C₄ -alkylene carboxylic acids, the correspondingC₆ -C₁₆ -alkylamino di-C₂ -C₄ -alkylene carboxylic acids and theirsalts, such as

C₁₂₋₁₄ H₂₅₋₂₉ NHCH₂ CH₂ COOH (Deriphat 170C)

and ##STR6##

The hydrocarbon nonionic surfactant, in addition to acting as aninterfacial tension depressant can serve as a stabilizer and solubilizerfor the AFFF compositions, particularly when they are diluted with hardwater or sea water. In addition, they serve to control foam drainage,foam viscosity and foam expansion. Suitable nonionic surfactants includepolyethoxylated (5 to 40 units) derivatives of: alkyl phenols, linear orbranched chain C₆ -C₁₆ alcohols, C₆ -C₁₆ alkyl mercaptans, C₆ -C₁₆alkanoic acids, C₆ -C₁₆ alkyl amines or amides, or polyethoxylatedpropylene oxides.

The solvent component (H) are alcohols or ethers as described in U.S.Pat. No. 4,090,967.

Preferred solvents are 1-butoxyethoxy-2-propanol, diethyleneglycolmonobutyl ether, hexylene glycol, or glycerol.

Component I is an electrolyte, typically a salt of a monovalent orpolyvalent metal of Groups 1, 2 or 3, or organic base.

Preferred are polyvalent salts such as magnesium sulfate, magnesiumnitrate or strontium nitrate.

High molecular weight foam stabilizers such as polyethyleneglycol,polyacrylamide, hydroxypropyl cellulose, or polyvinylpyrrolidonecomprise component K.

Component L are polysaccharides from natural sources which may have beenchemically modified. Preferred are heteropolysaccharides from bacterialfermentation which have been chemically modified.

The thixotropic polysaccharides are especially useful in compositionsused to fight hydrophilic organic liquid fires. Such compositions,suitable for fighting both hydrophobic and hydrophilic organic liquidfires, are termed in the art as universal AFFF agents. Suitablethixotropic agents include those polysaccharides disclosed in U.S. Pat.No. 3,915,800 or 4,149,599.

Still other components which may be present in the formula are:

Buffers whose nature is essentially non-restricted and which areexemplified by Sorensen's phosphate or McIlvaine's citrate buffers.

Corrosion inhibitors whose nature is non-restricted so long as they arecompatible with the other formulation ingredients.

Chelating agents whose nature is non-restricted, and which areexemplified by polyaminopolycarboxylic acid ethylenediaminetetraaceticacid, citric acid, tartaric acid, nitrilotriacetic acidhydroxyethylethylenediaminetriacetic acid and salts thereof. These areparticularly useful if the composition is sensitive to water hardness.

Bacteriostats whose nature is unrestricted, but are necessary ifpolysaccharides are present. They may be exemplified by orthophenylphenol.

The concentrates of this invention are effective fire fightingcompositions over a wide range of pH, but generally such concentratesare adjusted to a pH of 6 to 9, and more preferably to a pH of 7 to 8.5,with a dilute acid or alkali. For such purpose may be employed organicor mineral acids such as acetic acid, oxalic acid, sulfuric acid,phosphoric acid and the like or metal hydroxides or amines such assodium or potassium hydroxides, triethanolamine, tetramethylammoniumhydroxide and the like.

As mentioned above, the compositions of this invention are concentrateswhich must be diluted with water before they are employed as firefighting agents. Although at the present time the most practical, andtherefore preferred, concentrations of said composition in water are 3%and 6% because of the availability of fire fighting equipment which canautomatically admix the concentrate with water in such proportions,there is no reason why the concentrate could not be employed in lowerconcentrations of from 0.5% to 3% or in higher concentrations of from 6%to 12%. It is simply a matter of convenience, the nature of fire and thedesired effectiveness in extinguishing the flames.

An aqueous AFFF concentrate composition which would be very useful in a6% proportioning system comprises

D. 0.05 to 0.3% by weight of an R_(f).R_(f) complex.

E. 0 to 30% by weight of fluorochemical surfactants.

F. 0.1 to 0.3% by weight of fluorochemical synergist.

G. 0.05 to 3% by weight of hydrocarbon surfactant.

H. 0 to 25% by weight of solvent.

I. 0 to 2% by weight of electrolyte.

K. 0 to 2% by weight of foam stabilizer.

L. 0 to 5% by weight of polysaccharide.

M. Water in the amount to make up the balance of 100%.

Each component D to M may consist of a specific compound or mixtures ocompounds.

The subject composition can be also readily dispensed from an aerosoltype container by employing a conventional inert propellant such asFreon 11, 12, N₂ or air. Expansion volumes as high as 50 based on theratio of air to liquid are attainable.

The major element of the AFFF system of this invention is the presenceof the instant R_(f).R_(f) complexes.

The above compositions are concentrates which, as noted above, whendiluted with water, form very effective fire fighting formulations byforming a foam which deposits a tough film over the surface of theflammable liquid which prevents its further vaporization and thusextinguishes the fire.

It is a preferred fire extinguishing agent for flammable solvent fires,particularly for hydrocarbons and polar solvents of low watersolubility, in particular for:

Hydrocarbon Fuels--such as gasoline, heptane, toluene, hexane, Avgas,VMP naphtha, cyclohexane, turpentine and benzene;

Polar Solvents of Low Water Solubility--such as butyl acetate, methylisobutyl ketone, butanol, ethyl acetate, and

Polar Solvents of High Water Solubility--such as methanol, acetone,isopropanol, methyl ethyl ketone, ethyl cellosolve and the like.

It may be used concomitantly or successively with flame suppressing drychemical powders such as sodium or potassium bicarbonate, ammoniumdihydrogen phosphate, CO₂ gas under pressure, or Purple K, as inso-called Twin-agent systems. A dry chemical to AFFF agent ratio wouldbe from 10 to 30 lbs. of dry chemical to 2 to 10 gallons AFFF agent atuse concentration (i.e. after 0.5%, 1%, 3%, 6% or 12% proportioning). Ina typical example 20 lbs. of a dry chemical and 5 gals. of AFFF agentcould be used. The composition of this invention could also be used inconjunction with hydrolyzed protein or fluoroprotein foams.

The foams of the instant invention do not disintegrate or otherwiseadversely react with a dry powder such as Purple-K Powder (P-K-P).Purple-K Powder is a term used to designate a potassium bicarbonate fireextinguishing agent which is free-flowing and easily sprayed as a powdercloud on flammable liquid and other fires.

The concentrate is normally diluted with water by using a proportioningsystem such as, for example, a 3% or 6% proportioning system whereby 3parts or 6 parts of the concentrate is admixed with 97 or 94 parts,respectively, of water. This highly diluted aqueous composition is thenused to extinguish and secure the fire.

Today's commercial AFFF agents are only capable for use on 6, 3 and 1%proportioning systems. The compositions of the instant AFFF agents andthe ranges of the amounts of the different active ingredients in thesenovel AFFF agents can be expressed for 0.5 to 12% proportioning systems.If the concentration in a composition for 6% proportioning is doubledthen such a concentrate can be used for a 3% proportioning system.Similarly, if the concentration of such a 6% proportioning system isincreased by a factor of 6 then it can be used as a 1% proportioningsystem.

EXPERIMENTAL PART

The following examples are illustrative of various representativeembodiments of the invention, and are not to be interpreted as limitingthe scope of the appended claims. In the examples, all parts are byweight unless otherwise specified.

Examples 1 through 10 illustrate the synthesis of the novel R_(f) R_(f)ion-pair complexes as well as their efficiency as surface tensiondepressants in comparison with their precursor anionic and cationicfluorochemical surfactants (Tables 2 through 5).

Example 11 demonstrates the utility of the novel R_(f) R_(f) ion-paircomplexes as oil and water repellent finishes for paper and textiles.

Tables 6 through 12 list the key components used for the formulation ofpreferred R_(f) R_(f) ion-pair complex-based AFFF agents, namely (a)selected R_(f) R_(f) ion-pair complexes (Table 6), (b) selectedfluorochemical surfactants (Table 7), (c) selected fluorochemicalsynergists (Table 8), (d) selected hydrocarbon surfactants (Table 9),(e) selected solvents (Table 10), (f) selected electrolytes (Table 11)and (g) selected foam stabilizers (Table 12).

Examples 12 through 27 show selected AFFF compositions derived from keycomponents as listed in Tables 6 through 12, as well as comparativeperformance data obtained with and without R_(f) R_(f) ion-paircomplexes present in the AFFF agent compositions.

In the examples, references are made to specifications used by theindustry and primarily the military and to proprietary tests to evaluatethe efficiency of selected compositions. More specifically, the examplesrefer to the following specifications and laboratory test method:

1. Surface Tension and Interfacial Tension--ASTM D-1331-56

2. Laboratory Sealability Test

Objective: To measure the ability of a fluorochemical AFFF formulation(at the end use concentration) to form a film across, and seal acyclohexane surface.

Procedure: Ten mls of cyclohexane is pipetted into a 48 mm evaporatingdish in the evaporometer cell. Helium flowing at 1000 cc per minuteflushes the cyclohexane vapors from the cell through a 3 cm IR gas cellmounted on a PE 257 infrared spectrophotometer (a recording infraredspectrophotometer with time drive capability). The IR absorbance of thegas stream in the region of 2850 cm⁻¹ is continuously monitored assolutions of formulations are infused onto the surface. Formulations areinfused onto the cyclohexane surface at a rate of 0.17 ml per minuteusing a syringe pump driven 1 cc tuberculin syringe fitted with a 13 cm22 gauge needle, whose needle is just touching the cyclohexane surface.

Once the absorbance for "unsealed" cyclohexane is established, thesyringe pump is started. Time zero is when the very first drop offormulation solution hits the surface. The time of 50% seal, percentseal at 30 seconds and 1-4 minutes are recorded. Time to 50% sealrelates well to film speed (see below), percent seal in 30 seconds and1-4 minutes relate well to the efficiency and effectiveness of the filmas a vapor barrier (film persistence).

3. Field Fire Tests As Defined in MIL-24385B for Aqueous Film FormingFoam

The most critical test of the subject compositions is actual fire tests.The detailed procedures for such tests on 28, 50 square foot fires areset forth in the U.S. Navy Specification MIL-F-24385B.

Procedure: Premixes of the compositions of this invention are preparedfrom 0.5 to 12% proportioning concentrates with tap or sea water, or theAFFF agent is proportioned by means of an in-line proportioning educatorsystem. The test formulation in any event is applied at an appropriateuse concentration.

The efficacy of the compositions of the present invention to extinguishhydrocarbon fires was proven repeatedly and reproducibly on 28-squarefoot (2.60 sq. m) and on 50-square feet (4.65 sq. meter) gasoline fires.The fire performance tests and subsidiary tests--foamability, filmformation, sealability, film speed, viscosity, drainage time, spreadingcoefficient, and stability, all confirmed that the compositions of thisinvention performed better than prior art AFFF compositions.

The most important criteria in determining the effectiveness of a firefighting composition are:

1. Control Time--The time to bring the fire under control or secure itafter a fire fighting agent has been applied.

2. Extinguishing Time--The time from the initial application to thepoint when the fire is completely extinguished.

3. Burn-Back Time--The time from the point when the flame has beencompletely extinguished to the time when the hydrocarbon liquidsubstantially reignites when the surface is subjected to an open flame.

4. Summation of % Fire Extinguished--When 50 square foot (4.645 sq. m.)fires are extinguished the total of the "percent of fire extinguished"values are recorded at 10, 20, 30 and 40 second intervals. Presentspecification for 50 square foot fires require the "Summation" to firesbe 300 or greater.

28-Square-Foot Fire Test

This test was conducted in a level circular pan 6 feet (1.83 m) indiameter (28 square feet--2.60 square maters), fabricated from 1/4"(0.635 cm) thick steel and having sides 5" (12.70 cm) high, resulting ina freeboard of approximately 21/2" (6.35 cm) during tests. The pan waswithout leaks so as to contain gasoline on a substrate of water. Thewater depth was held to a minimum, and used only to ensure completecoverage of the pan with fuel. The nozzle used for applying agent had aflow rate of 2.0 gallons per (g.p.m.) (7.57 l per minute) at 100 poundsper square inch (p.s.i.) (7.03 kg/sq. cm) pressure. The outlet wasmodified by a "wing-tip" spreader having a 1/8" (3,175 mm) wide circulararc orifice 17/8" (7.76 cm) long.

The premix solution in fresh water or sea water was at 70°+-10° F. (21°C.+-5.5° C.). The extinguishing agent consisted of a 6-percentproportioning concentrate or its equivalent in fresh water or sea waterand the fuel charge was 10 gallons (37.85 l) of gasoline. The completefuel charge was dumped into the diked area within a 60-second timeperiod and the fuel was ignited within 60 seconds after completion offueling and permitted to burn freely for 15 seconds before theapplication of the extinguishing agent. The fire was extinguished asrapidly as possible by maintaining the nozzle 31/2 to 4 feet above theground and angled upward at a distance that permitted the closest edgeof the foam pattern to fall on the nearest edge of the fire. When thefire was extinguished, the time-for-extinguishment was recordedcontinuing distribution of the agent over the test area until exactly 3gallons (11.36 l) of premix has been applied (90-second applicationtime).

The burnback test was started within 30 seconds after the 90-secondsolution application. A weighted 1-foot (30.48 cm) diameter pan having2" (5.08 cm) side walls and charged with 1 quart (0.046 l) of gasolinewas placed in the center of the area. The fuel in the pan was ignitedjust prior to placement. Burnback time commenced at the time of thisplacement and terminated when 25 percent of the fuel area (7 squarefeet--0.65 sq. meter), (36-inch diameter--232.26 sq. cm), originallycovered with foam was aflame. After the large test pan area sustainedburning, the small pan was removed.

EXAMPLE 13-(1,1,2,2-tetrahydroperfluorooctylthio)-2-hydroxypropyltrimethylammonium2-methyl-2-(3-[1,1,2,2-tetrahydroperfluorooctylthio]propanesulfonate C₆F₁₃ CH₂ CH₂ SCH₂ CH₂ CONHC(CH₃)₂ CH₂ SO₃.sup.⊖.N.sup.⊕ (CH₃)₃ CH₂CHOHCH₂ SCH₂ CH₂ C₆ F₁₃

Sodium2-methyl-2-(3-[1,1,2,2-tetrahydroperfluorooctylthio]-propionamide)-1-propanesulfonate(42.0 gms, 30% actives, 0.02 moles, and3-(1,1,2,2-tetra-hydroperfluorooctylthio)-2-hydroxypropyltrimethylammoniumchloride (39.0 gms, 28.7% actives, 0.02 moles) were combined anddialyzed for 48 hours in distilled water in a commercially availableseamless dialysis tubes made from regnerated cellulose, 64 mm flatwidth.

The product was obtained by evaporating the contents of the dialysis bagin a draft oven at 60° C. The product was washed with several liters ofdistilled water, re-evaporated and then thoroughly dried under highvacuum. It was obtained in essentially quantitative yield and slowlycrystallized to a m.p. 74°-98°.

Analysis for C₂₉ H₃₆ F₂₆ N₂ O₅ S₃ : Calc.: C, 32.16; H, 3.35; F, 45.61;N, 2.59. Found: C, 31.96; H, 3.22; F, 45.26; N, 2.48.

In the following examples, the specified R_(f) -anionic and R_(f)-cationic surfactants were combined and dialyzed in a similar fashion toExample 1. The products were all obtained in near quantitative yield.

EXAMPLE 2

Sodium2-methyl-2-(3-[1,1,2,2-tetrahydroperfluorooctylthio]-propionamido)-1-propanesulfonate(1.22 gms, 2 millimoles) was combined in the manner of Example 1, withN-1,1,2,2-tetrahydroperfluorodecyl pyridinium iodide. The product is awhite solid having a m.p. of 112°-113.5° C., of the structure ##STR7##

Analysis for C₃₀ H₂₆ F₃₀ N₂ O₄ S₂ : Calculated: C, 32.39; H, 2.36; F,51.23; N, 2.52; S, 5.76. Found: C, 32.45; H, 2.41; F, 51.18; N, 2.51; S,6.15.

EXAMPLE 3

Sodium2-methyl-2-(3-[1,1,2,2-tetrahydroperfluorooctylthio]-propionamide)-1-propanesulfonate(0.61 gm, 1 millimole) was reacted, in the manner according to Example1, with N-1,1,2,2-tetrahydroperfluorooctyl pyridinium iodide (0.55 gms,1 millimole).

The product is an off-white solid having an m.p. of 88.0°-90.5° C. Theproduct is of the structure ##STR8##

Analysis for C₂₈ H₂₆ F₂₆ N₂ O₄ S₂ : Calculated: C, 33.21; H, 2.59; F,48.78; N, 2.77; S, 6.33. Found: C, 33.23; H, 2.38; F, 48.05; N, 2.75; S,6.64.

EXAMPLE 4

Sodium2-methyl-2-(3-[1,1,2,2-tetrahydroperfluorooctylthio]propionamido)-1-propanesulfonate(1.22 gms, 2 millimoles) was reacted, in the manner according to Example1, with N-[perfluorooctylsulfonamido)propyl]-N,N,N-trimethylammoniumiodide (1.45 gms, 2 millimoles). The product is a tan solid having anm.p. of 133°-140° C. The product has the structure

    C.sub.6 F.sub.13 CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 CONHC(CH.sub.3).sub.2 CH.sub.2 SO.sub.3.sup.⊖.N.sup.⊕ (CH.sub.3).sub.3 CH.sub.2 CH.sub.2 CH.sub.2 NHSO.sub.2 C.sub.8 F.sub.17

Analysis for C₂₉ H₃₃ F₃₀ N₃ O₆ S₃ : Calculated: C, 29.38; H, 2.81; F,48.07; N, 3.54; S, 8.11. Found: C, 29.47; H, 2.85; F, 47.86; N, 3.50; S,8.29.

EXAMPLE 5

Sodium2-methyl-2-(3-[1,1,2,2-tetrahydroperfluoroalkylthio]propionamido)-1-propanesulfonatewherein perfluoroalkyl has an R_(f) distribution of 49% C₆, 49% C₈ and2% C₁₀, was reacted, according to the manner of Example 1, with anequimolar amount ofN-(3-[1,1,2,2-tetrahydroperfluoroalkylthio]-2-hydroxypropyl)-N,N,N-trimethylammonium chloride wherein the perfluoroalkyl has an R_(f) distributionof 49% C₆, 49% C₈ and 2% C₁₀. The product is a white solid which softensat 85° C. and has an m.p. of 148°-155° C. The product has the structure

    R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 CONHC(CH.sub.3).sub.2 CH.sub.2 SO.sub.3.sup.⊖.N.sup.⊕ (CH.sub.3).sub.3 CH.sub.2 CHOHCH.sub.2 SCH.sub.2 CH.sub.2 R.sub.f

EXAMPLE 6

The products of Examples 1, 2 and 4 were tested for their respectivesolubility in distilled water. The R_(f).R_(f) complexes exhibit thefollowing solubility in weight %:

Example 1: 5×10⁻³

Example 2: 1.2×10⁻³

Example 4: 1×10⁻³

None of the R_(f).R_(f) complexes of Examples 1, 2 and 4 exhibitedmicellar behavior. The concentrated solutions of Example 1 and 2 exhibita surface tension of 16.9 and 17.5 dynes/cm, respectively.

EXAMPLE 7

Anionic and cationic fluorochemical surfactants as listed in Table 2awere reacted in various molar ratios as shown in Table 2b. The surfacetensions measured at 0.1% and 0.01% total actives as listed in Table 2bindicate, that the results obtained with equimolar mixtures of theanionic and cationic surfactants (quantitative yield of R_(f) R_(f) ionpair complex) provide the lowest surface tension. Similarly it is shownin Table 3, that the R_(f) R_(f) ion pair complexes are superior surfacetension depressants as compared with the precursor anionic and cationicsurfactants. Data in Table 3 also indicate that fluorochemicalsurfactants with selected R_(f) -chains or homolog distributions havepreferred properties. The combination A2/C2 in Table 3 exhibits thelowest surface tensions ever reported at such a low concentration of afluorochemical surface tension sepressant (26.9 dynes/cm at 0.001% byweight of the R_(f) R_(f) ion-pair complex).

                                      TABLE 2a                                    __________________________________________________________________________    R.sub. f Surfactant                                                                  Name               Formula/R.sub.f Composition                         __________________________________________________________________________    Fluorinated Anionic Surfactants                                                                         R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                  CONHC(CH.sub.3).sub.2 CH.sub.2 SO.sub.3 Na                                    wherein:                                                                      % C.sub. 6 F.sub.13                                                                  % C.sub.8 F.sub.17                                                                   % C.sub.10 F.sub.21                                                                 % C.sub.12 F.sub.26             A1     2-Methyl-2-(3-1,1,2,2,-tetrahydro-                                                               33     36     22    6                                      perfluoroalkylthio propionamide)-1- -                                                            propanesulfonic acid, sodium salt                   A2     as above           44     49      1                                    A3     as above, 45%      100                                                 __________________________________________________________________________    Fluorinated Cationic Surfactants                                                                        R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2 CHOHCH.sub.2                              .sup.+N(CH.sub.3)Cl.sup.- wherein:                                            % C.sub.6 F.sub.13                                                                   % C.sub.8 F.sub.17                                                                   % C.sub.10 F.sub.21                                                                 % C.sub.12 F.sub.26             C1     3-(1,1,2,2-tetrahydroperfluoro-                                                                  33     36     22                                           alkylthio)-2-hydroxypropyl-                                                   trimethylammonium chloride                                             C2     as above           49     49      1                                    C3     as above, 45%      100                                                 __________________________________________________________________________

                  TABLE 2b                                                        ______________________________________                                         Surface Tension Effect of Varied Mole Ratios of Anionic and                  Cationic Fluorochemical Surfactants                                                     Mol. %    Mol.                                                                Anionic   % Cationic                                                          Fluorochemical                                                                          Fluorochemical                                                                            Surface                                                 Surfactant A1                                                                           Surfactant C1                                                                             Tension                                       ______________________________________                                        0.1% Total Actives                                                                        100          0          27.1                                                  75          25          21.9                                                  50          50          16.9                                                  25          75          18.7                                                   0          100         21.6                                      0.01% Total Actives                                                                       100          0          29.1                                                  75          25          23.5                                                  50          50          17.6                                                  25          75          22.3                                                   0          100         31.0                                      ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Surface Tension Data at                                                       Various Concentrations of Anionic and Cationic                                Fluorochemical Surfactants and Their R.sub.f.R.sub.f Complexes                Fluorochemical                                                                           1.0%   0.1%     0.01% 0.001% 0.0001%                               ______________________________________                                        A1         26.0   27.1     29.1  40.1                                         A2         25.6   24.5     24.4  41.7   69.8                                  C1         19.5   21.6     28.1  49.6   67.4                                  C2         20.5   20.0     29.6  52.3   66.6                                  A1/C1                      17.4.sup.a                                                                          55.1                                         A2/C2             16.1     16.1  26.9   56.6                                  ______________________________________                                         .sup.a ppt (24.3 at 0.005%)                                              

Analogous results are obtained when the salt of A3 and C1, C2 and C3 areprepared, as well as those of A1 and A2 with C3.

EXAMPLE 8

In the following equimolar amounts of A3 as specified in Example 7 isreacted according to the procedure as set forth in Example 1 with eachof C4, C5, C6, C7, C8, C9, C10 and C11. ##STR9## The resultingR_(f).R_(f) complexes, in each case, exhibit the desirable aqueoussurface tension reduction characteristics at low concentrations.

EXAMPLE 9

R_(f) R_(f) ion-pair complexes were synthesized from commercial anionicand cationic fluorochemical surfactants as listed in Table 4. Surfacetension comparisons of the precursor fluorochemical surfactants at 0.01%by weight in water versus the R_(f) R_(f) ion pair complexes at 0.01% byweight in water show, that the R_(f) R_(f) ion pair complexes providegenerally lower surface tension than the precursor fluorochemicalsurfactants.

                  TABLE 4                                                         ______________________________________                                        Surface Tension Values of Various Cationic/Anionic                            Ion Pair Complexes                                                            Cationic     Cationic/Anionic                                                                           Anionic                                             Surfactant Alone                                                                           Ion Pair Complex                                                                           Surfactant Alone                                    at 0.01%     at 0.01%     at 0.01%                                            ______________________________________                                        LODYNE S-106 28.1                                                                          16.8         LODYNE S-102 29.0                                   LODYNE S-106 28.1                                                                          16.3         LODYNE S-112 20.2                                   LODYNE S-106 28.1                                                                          18.6         FC 95 42.2                                          LODYNE S-106 28.1                                                                          17.9         FC 128 24.7                                         LODYNE S-106 28.1                                                                          19.6         Zonyl FSE 23.5                                      LODYNE S-106 28.1                                                                          23.9         Zonyl FSJ 24.9                                      LODYNE S-106 28.1                                                                          24.9         Monflor 31 29.5                                     Zonyl FSC 27.5                                                                             16.5         LODYNE S-102 29.0                                   Zonyl FSC 27.5                                                                             16.5         FC 128 24.7                                         Zonyl FSC 27.5                                                                             24.3         Zonyl FSJ 24.9                                      Zonyl FSC 27.5                                                                             22.3         Monflor 31 29.5                                     Monflor 71 47.1                                                                            25.6         Monflor 31 29.5                                     LODYNE S-116 20.3                                                                          16.1         LODYNE S-102 29.0                                   LODYNE S-116 20.3                                                                          16.5         LODYNE S-112 20.2                                   FC-134 17.8  17.2         LODYNE S-102 29.0                                   FC-134 17.8  16.7         FC 128 24.7                                         ______________________________________                                    

EXAMPLE 10

Table 5 shows the high efficiency of R_(f) R_(f) ion pair complexes assurface tension depressants as a function of concentration in water. Italso shows the high effectiveness of the complexes as measured by theminimum value to which it can lower the surface tension. The efficiencyand effectiveness of the subject cationic anionic complexes both areappreciably better than the commercial precursor fluorochemicalsurfactants.

                  TABLE 5                                                         ______________________________________                                        Surface Tension Values of R.sub.f R.sub.f Ion-Pair Complexes                  at Various Concentrations                                                     Cationic  R.sub.f R.sub.f                                                     Surfactant                                                                              Ion Pair  Anionic Surfactant                                        ______________________________________                                        0.001%                                                                              0.01%   0.0005%   .001% 0.0055%                                                                              0.01%                                    Cl 49.6                                                                             28.1    28.7      --    --     42.2  FC-95                                            21.8      --    --     24.7  FC-128                                           27.3      --    29.0   21.2  Zonyl                                                                         FSP                                              25.3      40.1  28.1   29.1  Al                                 ______________________________________                                    

EXAMPLE 11

The R_(f) -cationic/R_(f) -anionic ion pair complexes demonstrate oilrepellency when applied as a paper size or as a textile finish.

Paper Size--Dry paper pulp is diluted with water and to this suspensionare added a dilute solution of the R_(f).R_(f) complex prepared from A1and C1. Adjuvants are added and the slurry is then cast as a paper mat.After drying, this sheet gives a 3M oil repellency kit rating of 4 at0.06% fluorine on weight of paper [Kit No. 4=70 parts castor oil/15parts toluene/15 parts heptane].

Textile Finish--A solution of the R_(f).R_(f) complex prepared from A1and C1 was applied in a pad bath to 65/35 polyester cotton twill. At aconcentration of 0.06% F on the dry fabric in the presence of apermanent press finish, the swatch gave an AATCC oil repellency ratingof 3.

                                      TABLE 6                                     __________________________________________________________________________    R.sub.f .R.sub.f Complexes                                                    R.sub.f .R.sub.f                                                              Complexes                                                                           Name                Formula                                             __________________________________________________________________________                              R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2 CONHC(CH.sub                              .3).sub.2 CH.sub.2 SO.sub.3.sup.⊖.N.sup.                              ⊕ (CH.sub.3).sub.3 CHOHCH.sub.2 SCH.sub.2                                 CH.sub.2 R.sub.f                                                              wherein;                                                                      Anionic Segment   Cationic Segment                                            % C.sub.6 F.sub.13                                                                     % C.sub.8 F.sub.17                                                                     % C.sub.6 F.sub.13                                                                      % C.sub.8 F.sub.17      D1    3-(1,1,2,2-tetrahydroperfluoroalkylthio)-                                                         50       50       20        80                            2-hydroxy propyltrimethylammonium                                             2-methyl-2-(3[1,1,2,2-tetrahydroperfluoro-                                    alkylthio]propionamide)-1-propane sulfonate                             D2    As above            50       50       95        --                      D3    As above            95       --       95        --                      D4    As above            20       80       20        80                      D5    As above            95       --       20        80                      D6    As above            20       80       95        --                      D7    As above            95       --       50        50                      D8    As above            20       80       50        50                      __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________    Fluorinated Surfactants                                                       R.sub.f                                                                       Surfactant                                                                            Name                       Formula                                    __________________________________________________________________________                                       R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2                                           CH.sub.2 CONHC(CH.sub.3).sub.2                                                CH.sub.2 SO.sub.3 Na wherein;                                                 % C.sub.6 F.sub.13                                                                     % C.sub.8 F.sub.17                                                                      %                                                                             C.sub.10 F.sub.21       E1      2-Methyl-2-(3-[1,1,2,2-tetrahydroperfluoroalkylthio]                                                     40       42        12                              propanamide)-2-propanesulfonic acid; sodium salt                      E2      As above                   50       50        --                      E3      As above                   95       --        --                      E4      As above                   20       80        --                      E5      As above                   33       36        23                      E6      As above                   --       11        60                      E7      Perfluoroalkylthio oligomer                                                                              (as in copending application Ser. No.                                         129,872 filed 3/13/80)                     __________________________________________________________________________

                  TABLE 8                                                         ______________________________________                                        R.sub.f Synergists                                                            R.sub.f                                                                       Synergist                                                                            Name           Formula                                                 ______________________________________                                                         R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 CONH.sub.2                      wherein;                                                                            % C.sub.6 F.sub.13                                                                     % C.sub.8 F.sub.17                                                                   % C.sub.10 F.sub.21                     F1     3-[1,1,2,2-tetrahydro-                                                                       74       17      2                                             perfluoroalkylthio-]                                                          propionamide                                                           F2     As above       95        2     --                                      F3     As above       35       36     20                                      ______________________________________                                    

                                      TABLE 9                                     __________________________________________________________________________    Hydrocarbon Surfactants                                                       Hydrocarbon                                                                          Name                                                                   Surfactants                                                                          % Actives as Noted or ˜100%                                                                       Formula of Commercial Name                   __________________________________________________________________________    G1     Partial sodium salt of N--alkyl β-iminodipropionic                                                 wherein: R--                                        acid, 30%                 C.sub.12 H.sub.25 (Deriphat 160C,                                             General Mills)                               G2     Sodium alkyl sulfate      A 50/50 mixture of C.sub.8 H.sub.17 and                                       C.sub.10 H.sub.21                            G3     Disodium salt of N--alkyl-N,N-- bis(2-propionamide-                                                     RN[CH.sub.2 CH.sub.2 CONHC(CH.sub.3).sub.                                     2 CH.sub.2 SO.sub.3 Na].sub.2                       2-methyl-1-propane sulfonate                                                                            wherein: R is                                                                 C.sub.8 H.sub.17                             G4     As above                  As above wherein R = C.sub.6 H.sub.13                                         OCH.sub.2 CH.sub.2 CH.sub.2 --               G5     Octylphenoxypolyethoxyethanol (12) 99%                                                                  Triton X-102, Rohm & Haas                    G6     Polyoxyethylene (23) lauryl ether                                                                       Brij 35, I.C.I.                              __________________________________________________________________________

                  TABLE 10                                                        ______________________________________                                        Solvents                                                                      Solvents     Name                                                             ______________________________________                                        H1           1-butoxyethoxy-2-propanol                                        H2           2-methyl-2,4-pentanediol                                         H3           Ethylene glycol                                                  H4           Diethylene glycol monobutyl ether                                H5           Glycerine                                                        H6           Propylene glycol                                                 ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                        Electrolytes                                                                  Electrolyte  Name                                                             ______________________________________                                        I1           magnesium sulfate                                                I2           magnesium nitrate                                                I3           strontium nitrate                                                ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                        Foam Stabilizers                                                              Foam Stabilizers                                                                            Name                                                            ______________________________________                                        K1            polyethylene glycol                                             K2            hydroxypropyl cellulose                                         K3            polyvinyl pyrrolidone                                           ______________________________________                                    

EXAMPLES 12 AND 13

A comparison was made between AFFF compositions with regard tolaboratory performance. As noted below the formulation with theR_(f).R_(f) complex was appreciably faster at normal use dilution andhad a significantly lower surface tension even under high dilution.

                                      TABLE 13                                    __________________________________________________________________________                          No.      %                                              __________________________________________________________________________    AFFF Component                                                                R.sub.f R.sub.f complex                                                                             D2       Variable                                       R.sub.f surfactant    E2       0.75                                           R.sub.f synergist     F2       0.1                                            R.sub.h surfactant    G1 + G3 + G5                                                                           0.75 + 1.01 + 0.60                             Solvent               H4 + H6  14.0 + 8.0                                     MgSO.sub.4            I1       0.24                                           Water                          Balance                                        Example Number        12       13                                             R.sub.f.R.sub.f complex, %                                                                          None     0.006                                          Laboratory Performance                                                        Seal Speed (6% tap), sec                                                                            12       12                                             Seal Speed (6% sea), sec                                                                            24       20                                             Seal Speed (3% tap), sec                                                                            25       32                                             Seal Speed (3% sea), sec                                                                            50       56                                             Surface tension (3% distilled), dynes/cm                                                            20.7     18.1                                           Spreading coefficient (3% distilled), dynes/cm                                                       2.1      4.7                                           __________________________________________________________________________

EXAMPLES 14-17

Particularly well performing AFFF agents can be made by the judiciouschoice of R_(f).R_(f) complex and R_(h) surfactants

                                      TABLE 14                                    __________________________________________________________________________    AFFF Component                                                                             No.      %         %         %          %                        __________________________________________________________________________    R.sub.f R.sub.f complex                                                                    D2       .06       0.31      0.23       None                     R.sub.f surfactant                                                                         E2 + E7  1.12 + 0.4                                                                              0.88, --  1.08, --   0.90, --                 R.sub.f synergist                                                                          F2       0.19      0.18      0.20       0.15                     R.sub.h surfactant                                                                         G1 + G3 + G5                                                                           0.75 + 1.01 + 0.60                                                                      0.75 + 1.01 + 0.60                                                                      0.75 + 1.01 + 0.60                                                                       0.75 + 1.01 + 0.60       Solvent      H4 + H6  14.0 + 8.0                                                                              14.0 + 8.0                                                                              14.0 + 6.0  9.0 + 8.0               MgSO.sub.4   I1       0.24      0.24      0.24       0.24                     Water                 Balance   Balance   Balance    Balance                  __________________________________________________________________________    Example Number        14        15        16         17                       __________________________________________________________________________    Control Time, sec.    18        21        18         19                       Extinguishing Time, sec.                                                                            41        35        36.5       42                       40 Second Summation   341       336       350        323                      Burnback Time, min.   460       411       405        370                      Foam Expansion        8.5       7.7       8.3        8.2                      25% Drain Time, min.  300       301       286        251                      __________________________________________________________________________

EXAMPLES 18-19

AFFF concentrates containing polysaccharide were testedfor performanceon non-polar and polar (methanol) fires. The performance was quitesatisfactory in both regards.

                  TABLE 15                                                        ______________________________________                                        AFFF Components                                                                             No.          %                                                  ______________________________________                                        R.sub.f.R.sub.f complex                                                                     D2           0.06                                               R.sub.f surfactant                                                                          E2           0.72                                               R.sub.f synergist                                                                           F2           0.12                                               R.sub.h surfactant                                                                          G1 + G3 + G5 0.75 + 1.01 + 0.60                                 Solvent       H4 + H6      Variable                                           MgSO.sub.4    I1           0.24                                               Polysaccharide             Variable                                           Water                      Balance                                            ______________________________________                                        Example Number                                                                              18           19                                                 ______________________________________                                        Polysaccharide K8A13,                                                                       1.5          None                                               Solvent F4 + F6, %                                                                          10.0, None   14.0 + 8.0                                         ______________________________________                                        FIRE TESTS: 28 ft.sup.2                                                                     6T* on Gasoline                                                                            10T* on Methanol                                   ______________________________________                                        Control Time, sec                                                                           --           39                                                 Extinguishing Time, sec                                                                     23           62                                                 Burnback Time, min                                                                          12.8         22.8                                               Foam Expansion                                                                              6.9          7.4                                                25% Drain Time, min                                                                         25.3         53.5                                               ______________________________________                                         *6T indicates tap water containing 6% of AFFF concentrate 10T indicates       tap water containing 10% of AFFF concentrate                             

EXAMPLES 20-21

Large scale fire tests on 50 ft² fires were run on compositionsdiffering only with regard to the presence of an R_(f).R_(f) complex. Asnoted, the formulations with the complex had a more rapid fire knockdownas well as improved burnback performance and expansion.

                  TABLE 16                                                        ______________________________________                                        AFFF Components                                                                             No.          %                                                  ______________________________________                                        R.sub.f.R.sub.f complex                                                                     D2           Variable                                           R.sub.f surfactant                                                                          E2           0.67                                               R.sub.f synergist                                                                           F2           0.12                                               R.sub.h surfactant                                                                          G1 + G3 + G5 0.75 + 1.01 + 0.60                                 Solvent       H4 + H6      9.0 + 8.0                                          Water                      Balance                                            ______________________________________                                        Example Number                                                                              20           21                                                 ______________________________________                                        R.sub.f.R.sub.f complex, %                                                                  None         0.08                                               ______________________________________                                        FIRE TEST: 50 ft.sup.2,                                                       ______________________________________                                        Control Time, sec.                                                                          25-30        20-24                                              Extinguishing Time, sec.                                                                    48-54        44-50                                              Burnback Time, min.                                                                         301-346      357-373                                            Foam Expansion                                                                              6.1          6.8                                                Extinguishing Time -                                                                        288-298      317-323                                            40 sec. summation                                                             ______________________________________                                    

EXAMPLES 22-25

AFFF concentrates differing only with regard to the presence of anR_(f).R_(f) complex were tested for fish toxicity. A considerableimprovement was always found when the complex was present.

                  TABLE 17                                                        ______________________________________                                        AFFF Com-                                                                     ponent      Nr.          %                                                    ______________________________________                                        R.sub.f.R.sub.f complex                                                                   D2           Variable                                             R.sub.f surfactant                                                                        E2           Variable                                             R.sub.f synergist                                                                         F2           0.13                                                 R.sub.h surfactant                                                                        G1-2 + G3 + G5                                                                             Variable + 1.01 + 0.60                               Solvent     H4 + H6      14.0 + 8.0                                           MgSO.sub.4  I1           0.24                                                 Water                    Balance                                              ______________________________________                                        Example Number                                                                           22        23       24      25                                      ______________________________________                                        R.sub.f R.sub.f complex, %                                                               None      0.23     None    0.35                                    R.sub.f surfactant, %                                                                    0.75      0.63     0.75    0.63                                    R.sub.h surfactant, %                                                                    0.75 (G1) 0.75 (G1)                                                                              1.20 (G2)                                                                             1.20 (G2)                               ______________________________________                                        FISH TOXIC-                                                                   ITY                                                                           ______________________________________                                        LC.sub.50 -96 hr. ppm                                                                    2500-3000 >3000    3000-4000                                                                             >4000                                   ______________________________________                                    

EXAMPLES 26-27

In Examples 25 and 26 it is clearly shown that the R_(f).R_(f) complexappreciably aids fish toxicity of AFFF compositions.

                  TABLE 18                                                        ______________________________________                                        AFFF Components                                                                            No.           %                                                  ______________________________________                                        R.sub.f.R.sub.f complex                                                                    D2            Variable                                           R.sub.f surfactant                                                                         E2            Approx. 0.875                                      R.sub.f synergist                                                                          F2            0.15                                               R.sub.h surfactant                                                                         G1 + G3 + G5  0.75 + 1.01 + 0.60                                 Solvent      H4 + H6       9.0 + 8.0                                          MgSO.sub.4   I1            0.24                                               Water                      Balance                                            ______________________________________                                        Example Number                                                                             26            27                                                 ______________________________________                                        R.sub.f.R.sub.f complex, %                                                                 0.06          None                                               ______________________________________                                        FISH TOXICITY                                                                 ______________________________________                                        LC.sub.50 -96 hr, ppm                                                                      ˜5000   ˜2500                                        ______________________________________                                    

I claim:
 1. A hydrolytically stable ion pair complex of the formula

    R.sub.f --A--Q.sup.⊖.N.sup.⊕ (R.sub.1)(R.sub.2)(R.sub.3)--A'--R.sub.f '

wherein R_(f) and R_(f) ' independently represent perfluoroalkyl of 4 to12 carbon atoms; A and A' independently represent

    --CH.sub.2 CH.sub.2 --S--alkylene--G"--alkylene--

where G" is independently --SO₂ NH--, --CONH-- or ##STR10## and eachalkylene is straight or branched chain alkylene of 1 to 6 carbon atoms;R₁, R₂ and R₃ are independently hydrogen, phenyl, alkyl of 1 to 8 carbonatoms which is unsubstituted or is substituted by halo, hydroxy orphenyl; or is --CHR₄ CH₂ O)_(y) R₅ where y is 1 to 20, R₄ is hydrogen oralkyl of 1 to 4 carbon atoms and R₅ is hydrogen or methyl; or R₁ and R₂taken together with the nitrogen to which they are attached representpiperidino, morpholino or piperazino; or R₁, R₂ and R₃ taken togetherwith the nitrogen to which they are attached represent pyridinium orpyridinium substituted by alkyl of 1 to 4 carbon atoms; and Q representsthe carboxy, sulfo, phosphato or phosphono anion.
 2. An ion pair complexaccording to claim 1, wherein R₁, R₂ and R₃ are, methyl.
 3. An ion paircomplex according to claim 2, wherein Q is the sulfo, carboxy orphosphato anion.
 4. An ion pair complex according to claim 2 of theformula ##STR11## wherein R_(f) and R_(f) ' independently representperfluoroalkyl of 4 to 12 carbon atoms.